Thermoplastic polyurethane and associated method and article

Abstract

A thermoplastic polyurethane composition is formed by the reaction of a specific bifunctional poly(arylene ether) having an end group, wherein the end group comprises a linking group comprising a substituted or unsubstituted saturated hydrocarbylene group or a substituted or unsubstituted saturated poly(hydrocarbylene ether), and a terminal functional group comprising a hydroxyl group or a salt thereof, with an organic diisocyanate. The thermoplastic polyurethane compositions can exhibit improved dielectric properties. Methods for the manufacture of the thermoplastic polyurethane compositions and articles derived therefrom are also described.

Description

THERMOPLASTIC POLYURETHANE AND ASSOCIATED METHOD AND ARTICLECROSS REFERENCE TO RELATED APPLICATIONThis application claims priority to and the benefit of European Patent Application No. 24171642.2 filed April 22, 2024, the contents of which are hereby incorporated by reference in their entirety.BACKGROUND

[0001] This disclosure relates to thermoplastic polyurethanes, and in particular polyurethanes prepared from reaction of a particular bifunctional poly(arylene ether) and an organic diisocyanate, methods of manufacture, and uses thereof.

[0002] Thermoplastic polyurethanes (TPUs) are prepared from diols and diisocyanates. The isocyanate groups of the diisocyanate react with the hydroxyl groups on the diol to form a urethane linkage. The diol can be, for example, a low molecular weight polyether diol or polyester diol. The diisocyanate can be aliphatic or aromatic. The family of TPU resins is very complex because of the enormous variation in the compositional features of the diols and diisocyanates. This variety results in a large numbers of polymer structures and performance profiles. Indeed, TPUs can be rigid solids, or soft and elastomeric. TPUs are fully thermoplastic and can be melt-processed.

[0003] The generally recognized useful features of TPUs include high impact strength even at low temperatures, good abrasion resistance, good heat resistance, excellent resistance to non-polar solvents and fuels and oils, resistance to ozone and oxidation and humidity, and good electrical resistance. Less desirable features include high moisture absorption and lower rigidity at elevated temperatures.

[0004] There exists an opportunity for TPUs that exhibit improvements in one or more of the foregoing properties. It would be particularly advantageous to provide TPUs having improved dielectric properties, particularly for applications in electronic coatings, wire and cable coatings, and other applications requiring good insulating properties.SUMMARY

[0005] An aspect is a thermoplastic polyurethane composition comprising a thermoplastic polyurethane copolymer comprising a plurality of arylene ether repeat units derived from a bifunctional poly(arylene ether) comprising an end group, wherein the end group comprises a linking group comprising a substituted or unsubstituted saturated hydrocarbylenegroup or a substituted or unsubstituted saturated poly(hydrocarbylene ether), and a terminal functional group comprising a hydroxyl group or a salt thereof; and a plurality of diisocyanatederived repeat units; wherein at least one terminal oxygen atom of each arylene ether repeat unit is covalently bonded to a terminal carbamoyl group of a diisocyanate-derived repeat unit to form a urethane moiety; and wherein the composition comprises 0 to 5,000 ppm of a poly(arylene ether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof.

[0006] Another aspect is an article comprising the thermoplastic polyurethane composition.

[0007] Another aspect is a method of forming a thermoplastic polyurethane composition, the method comprising: reacting a bifunctional poly(arylene ether) comprising an end group, comprising a linking group comprising a substituted or unsubstituted saturated hydrocarbylene group or a substituted or unsubstituted saturated poly(hydrocarbylene ether), and a terminal functional group comprising a hydroxyl group or a salt thereof, with an organic diisocyanate to form a thermoplastic polyurethane composition.

[0008] The above described and other features are exemplified by the following detailed description.DETAILED DESCRIPTION

[0009] The present inventors have prepared a thermoplastic polyurethane composition the incorporates specific poly(arylene ether) segments and exhibits improvements in dielectric properties. Accordingly, a thermoplastic polyurethane composition represents one aspect of the present disclosure.

[0010] The thermoplastic polyurethane composition comprises a thermoplastic polyurethane copolymer comprising a plurality of arylene ether repeat units derived from a bifunctional poly(arylene ether) comprising an end group that includes a linking group that is a substituted or unsubstituted saturated hydrocarbylene group or a substituted or unsubstituted saturated poly(hydrocarbylene ether), and a terminal functional group comprising a hydroxy group or a salt thereof, and a plurality of diisocyanate-derived repeat units. As used herein, the term “plurality” means at least three. At least one terminal oxygen atom of each arylene ether repeat unit is covalently bonded to a terminal carbamoyl group of a diisocyanate-derived repeat unit to form a urethane moiety. Advantageously, the thermoplastic polyurethane composition comprises 0 to 5,000 ppm of repeating units derived from a poly(arylene ether) comprising alinking group comprising a carbonate functional group, an ester functional group, or a combination thereof.

[0011] Exemplary linking groups shown below include an unsubstituted saturated hydrocarbylene group, (e.g., an ethyl group structure on left) and an unsubstituted, saturated poly(hydrocarbylene ether) (e.g., diethyl ether; structure on right). The terminal functional group in both structures shown below is OH, and “> / vvv' ” indicates a link to the remaining portion of the bifunctional poly(arylene ether).

[0012] As will be discussed in further detail below, in addition to the illustrative end groups shown in the structures above, the substituted or unsubstituted saturated hydrocarbylene linking group includes a substituted or unsubstituted C2-30 hydrocarbylene group. The C2-30 hydrocarbylene group can include at least 2, at least 3, at least 4, or at least 6 carbons and up to 30, up to 20, up to 10, up to 8, up to 6, or up to 4 carbons. A range of carbon atoms in the hydrocarbylene group can include any of the foregoing limits. For example, the C2-30 hydrocarbylene group can include a substituted or unsubstituted C2-10 alkyl, preferably C2-4 alkyl, more preferably C2-3 alkyl group.

[0013] The substituted or unsubstituted saturated poly(hydrocarbylene ether) linking group can include a substituted or unsubstituted a C4-ioopoly(hydrocarbylene ether). The C4-100 poly(hydrocarbylene ether) can include at least 10, at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, at least 50, at least 55, or at least 60 carbons and up to 90, up to 80, up to 70, up to 60, up to 50, up to 40, up to 30, or up to 20 carbons. A range of carbon atoms in the poly (hydrocarbylene ether) can include any of the foregoing limits.

[0014] The C4-ioopoly(hydrocarbylene ether) can include a substituted or unsubstituted C4-ioopoly(C2-4 alkylene ether). The number of carbons in the C4-ioopoly(C2-4 alkylene ether) can include any of the above foregoing limits. In some aspects, the C4-ioopoly(hydrocarbylene ether) includes a C4-ioopoly(C2-3 alkylene ether). In certain aspects, the C4-100 poly(hydrocarbylene ether) includes a C4-ioopoly(C2 alkylene ether).

[0015] In an aspect, the plurality of arylene ether repeat units can have the structurewherein each occurrence of Q is independently halogen, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; each occurrence of Q2is independently hydrogen, halogen, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; each occurrence of R1and R2is independently hydrogen, halogen, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; each occurrence of R3and R4is independently hydrogen, halogen, or C1-18 alkyl; m and n are independently 0 to 20, provided that the sum of m and n is at least 3; x is independently at each occurrence 0 to 40, provided that at least one occurrence of x is 1 ; y is independently at each occurrence at least 1, preferably 1 to 3; and Y iswherein each occurrence of Ra, Rb, Rc, Rd, and Reis independently hydrogen, C1-12 hydrocarbyl, or Ci -6 hydrocarbylene, optionally wherein Raand Rbor Rcand Rdtogether are a C4-8 alkylene group; each occurrence of R7is independently hydrogen, a C1-14 hydrocarbyl, a C1-14 halohydrocarbyl, or a C1-14 heterohydrocarbyl, preferably C1-13 alkyl, C1-13 alkoxy, C2-13 alkenyl, C2-13 alkenyloxy, C3-6 cycloalkyl, C3-6 cycloalkoxy, Ce-i4 aryl, Ce-io aryloxy, C7-13 arylalkyl, C7-13 arylalkoxy, C7-13 alkylaryl, or C7-13 alkylaryloxy; each occurrence of R8is independently a C1-6 hydrocarbylene group, preferably a divalent C2-8 aliphatic group, more preferably dimethylene, trimethylene, or tetramethylene; and E is 2 to 200, 2 to 125, 5 to 125, 5 to 100, 5 to 50, 20 to 80, 10 to 60, or 5 to 20.

[0016] The term “hydrocarbyl”, whether used by itself, or as a prefix, suffix, or fragment of another term, refers to a residue that contains only carbon and hydrogen unless it is specifically identified as “substituted hydrocarbyl”. The hydrocarbyl residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain a combination of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. When the hydrocarbyl residue is described as substituted, it can contain heteroatoms in addition to carbon and hydrogen. For example, Q1can be a di-n- butylaminomethyl group formed by reaction of a terminal 3, 5 -dimethyl- 1,4-phenyl group with the di-n-butylamine component of an oxidative polymerization catalyst.

[0017] In an aspect, each occurrence of Q1is independently halogen, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl. In an aspect, each occurrence of Q2is independently hydrogen, halogen, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl. In an aspect, each occurrence of Q1is independently C1-12 alkyl, especially methyl. In an aspect, each occurrence of Q2is independently hydrogen or methyl.

[0018] Also in the poly(arylene ether) repeat unit structure, each occurrence of R1and R2is independently hydrogen, halogen, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl. In an aspect, each occurrence of R1is methyl, and each occurrence of R2is hydrogen. In general, m and n are independently 0 to 20, provided that the sum of m and n is at least 3. In an aspect, the sum of m and n is 4 to 16. aspect, Y iswherein each occurrence of R’ is independently hydrogen or Ci-Ce alkyl. In some aspects, each occurrence of R’ is methyl.

[0020] In an aspect, R3and R4are hydrogen. In an aspect, each occurrence of R3is hydrogen, and one occurrence of R4is hydrogen and one occurrence if R4is C1-6 alkyl,preferably methyl. In the foregoing formula, y is at least 1, preferably 1 to 3, and x is 1 or more, for example 1 to 25. In an aspect x is 1. In an aspect, y is 1.

[0021] In a specific aspect, the arylene ether repeat units have the structurewherein x is independently at each occurrence 0 to 15, preferably 0 to 1, provided that at least one occurrence of x is 1.

[0022] The bifunctional poly(arylene ether) is the product of oxidative copolymerization of monomers comprising a monohydric phenol, a dihydric phenol, or a combination thereof, to form a poly(arylene ether) having phenolic terminal groups, and subsequent reaction with an alkylene oxide to form the bifunctional poly(arylene ether).

[0023] The poly(arylene ether) having phenolic terminal groups can be formed by polymerization of monomers, for example, including a monohydric phenol, a dihydric phenol, or a combination thereof, by continuous addition of oxygen to a reaction mixture including the monomers, optionally a solvent, and a polymerization catalyst. The molecular oxygen (O2) can be provided as air or pure oxygen. The polymerization catalyst can be a metal complex, i.e. a metal catalyst, including a transition metal cation, including cations from Group VIB, VIIB, VIIIB, or IB of the periodic table, or a combination thereof. The catalyst can include a metal cation such as chromium, manganese, cobalt, copper, or combination thereof and an anion such as chloride, bromide, iodide, sulfate, acetate, propionate, butyrate, laurate, palmitate, benzoate, or a combination of one or more of these anions, and optionally one or more charge-neutral ligands such as water, amines, phosphines, CO, or the like. Alternatively, a metal or metal oxide and an inorganic acid, organic acid, or an aqueous solution of such an acid can be combined to form a corresponding metal salt or hydrate in situ. For example, cuprous oxide and hydrobromic acid can be combined to generate cuprous bromide in situ.

[0024] Exemplary amine ligands can be, for example, a monoamine, an alkylene diamine, or a combination thereof. Monoamines include dialkylmonoamines (such as di-n- butylamine) and trialkylmonoamines (such as N,N-dimethylbutylamine). Exemplary monoamines include di-n-butylamine, n-butylethylamine, di-tert-butylamine, tertbutylethylamine, dimethylamine, di-n-propylamine, di-sec-butyl amine, dipentylamine, dihexylamine, dioctylamine, didecylamine , dibenzylamine, methylethylamine, methylbutylamine, dicyclohexylamine, N-ethylaniline, N-butyl aniline, N-methyl-2-methylaniline, N-methyl-2,6-dimethylaniline, diphenylamine, or a combination thereof. Exemplary diamines include a N,N'-di-tert-butylethylenediamine, or the like, or a combination thereof. Exemplary trialkylmonoamines include trimethylamine, triethylamine, tripropylamine, tributylamine, butyldimethylamine, phenyldiethylamine, or the like, a combination thereof.

[0025] When the amine ligand includes a secondary amine such as di-n-butylamine, some of the secondary amine can be chemically incorporated into the poly(arylene ether) having phenolic terminal groups at the benzylic position of terminal monohydric phenol units. The covalently bound monoamine groups can be present as aminomethyl groups ortho to the phenol oxygen in terminal units as shown below:

[0026] The amount of covalently bound monoamine groups can be determined by1H- NMR spectroscopy. Covalently bound monoamine groups can adversely affect the oxidative stability of capped poly(arylene ether) and can result in yellowing of the capped poly(arylene ether) upon heat aging.

[0027] Poly(arylene ethers), for example, poly(phenylene ether), which optionally can be in the form of a copolymer of two or more monomers, for example a terpolymer, and the raw materials used to produce the poly(arylene ethers) can be, or can be formed from, renewable, sustainable, bio-circular, circular, lower carbon footprint feedstocks, upcycled, and / or postconsumer / post-industrial recycled materials, including pyrolysis oil (“py-oil”) .

[0028] Poly(arylene ethers) made from renewable sources can include, for example, a bio-content or PCR content of up to about 99.9%, about 1-99%, 5-95%, 55-99%, or 80-99%, 1- 50%, 1-25%, 1-15%, 1-10%, or 1-5%, based, e.g., on the monomer source. The poly(arylene ether) can be, e.g., an oligomer with as few as two repeating units to ultra-high molecular weight poly(arylene ethers). The weight average molecular weight of the poly(arylene ethers) in some aspects can be 600 to 200,000 grams per mole, as determined by gel permeation chromatography. In other aspects, the poly(arylene ethers) can have an intrinsic viscosity of up to 1.5 deciliters per gram (dl / g) as measured at 25 °C in chloroform. Poly( arylene ethers) made from renewable sources can include material made by a mass balance approach and certified by regulatory bodies such as, for example, the ISCC Plus.

[0029] Poly(arylene ethers) some aspects can be prepared by oxidative polymerization of monomers in the presence of a polymerization catalyst in the presence of oxygen. Any of the components used in the polymerization reaction or their synthetic precursors, or the solvents used in the process, can be bio-sourced, bio-circular, or renewable raw materials. Such components and precursors include monomers (e.g., monohydric phenol, dihydric phenol and other comonomers), reagents, solvents, catalysts (e.g., a metal source, a secondary alkylene diamine ligand, a tertiary monoamine, and optionally a secondary monoamine or alternatively enzyme catalysts), gases (e.g., oxygen gas), or a combination thereof. In some aspects, reaction components used in the polymerization of poly(arylene ethers) can be from sources as listed in the EU Renewable Energy Directive Annex IX.

[0030] Poly(arylene ethers) can be further processed, such as by redistribution, or any chemical derivatization, such as post-polymerization end-group capping or coupling, to make other materials that can transfer the sustainability characteristic to the new material. Such reagents and / or their synthetic precursors can be sustainable, bio-sourced, bio-circular, or renewable raw materials, upcycled, and / or post-consumer / post-industrial recycled materials, including pyrolysis oil (“py-oil”), to produce a poly(arylene ether).

[0031] Biosourced and sustainable materials can be derived from biomass sources or industrial sources such as waste (e.g., municipal waste). Biomass is a renewable organic material that comes from organic matter. Lignocellulosic biomass, the most abundant type of biomass and includes a wide variety of different biomass types including grasses, wood, energy crops, and agricultural and municipal wastes, is mostly composed of cellulose, hemicellulose, and lignin. Depolymerization of lignin, which is a phenolic polymer, can provide phenol. Solvents used in the production of monomers, such as methanol and acetone can be obtained from syngas, which is a product of the gasification of biomass.

[0032] Poly(arylene ether), such as a recycled poly(arylene ether) comprising an open- or closed-loop post-consumer recycled (“PCR”) poly(arylene ether), an open- or closed-loop post-industrial recycled (“PIR”) poly(arylene ether), or upcycled polyphenylene ether or a combination thereof can be used, provided that the desired property or combination of properties can be achieved. As used herein, the term “post-consumer recycle poly(arylene ether)” refers to a poly(arylene ether) that has reached the intended user or consumer and which has been collected or reclaimed after utilization by the end-user or consumer. Thus, for example, it is understood that that the term refers to a poly(arylene ether) material in whole or in part that would have otherwise been disposed of as waste, but has instead been collected and recovered (reclaimed) as a material input, in lieu of a virgin material, for a recycling or manufacturingprocess. PCR-poly(arylene ether) is inclusive of material that has been reprocessed from collected or reclaimed material by means of a manufacturing process, (including e.g., purification, sorting, and pretreating) and made into a product or into a component for incorporation into a product. Such recycled poly(arylene ether)s can be further processed, for example, into the form of powders, ground materials, flakes, pellets or other form. As used herein, the term “post-industrial recycled poly(arylene ether)” refers to a poly(arylene ether) polymer or polymers that have never reached the end user and that is production waste arising during polymerization reactions, during further processing, or during manufacturing the resin or an article and includes materials such as, but not limited to, sprues from injection molding, startup material from injection molding or extrusion, extrusion scrap, molding scrap, edge trims from extruded sheets or films, and the like, including materials diverted from the waste stream during a manufacturing process for an article.

[0033] In some aspects, the end groups are introduced by reacting the poly( arylene ether) having phenolic terminal groups with an alkylene oxide. The poly(arylene ether) having phenolic terminal groups can be converted to the metal salt by treatment with a base.

[0034] Suitable bases can include, for example alkali metal hydroxides (e.g., lithium hydroxide, sodium hydroxide, and potassium hydroxide), alkaline earth hydroxides (e.g., magnesium hydroxide and calcium hydroxide), non-nucleophilic bases (e.g., amines such as triethyl amine), alkali metal hydrides (e.g., lithium hydride, sodium hydride, and potassium hydride), and alkali metal carbonates (e.g., sodium carbonate or sodium bicarbonate). In a preferred aspect, the base includes sodium hydroxide or potassium hydroxide, more preferably potassium hydroxide. Both phenolic OH groups are converted to a phenoxide salt when combined with the base.

[0035] The base can be added in an amount of 1 to 10 mole percent, based on the total moles of the bifunctional poly(arylene ether) hydroxyl groups. Within this range, the base can be added in an amount of 2 to 7 mole percent, or 4 to 6 mole percent, each based on the total moles of the bifunctional poly (arylene ether) hydroxyl groups.

[0036] In some aspects, the poly(arylene ether) having phenolic terminal groups can be reacted with a capping agent comprising an alkylene oxide of the formulawherein p is 1-3, preferably 1-2 and R19is hydrogen or Ci-is primary alkyl, preferably hydrogen or Ci-6 alkyl, more preferably hydrogen or C1-3 alkyl. In some aspects, p is 1-3, R19is hydrogen or methyl, preferably p is 1-2 and R19is hydrogen, more preferably p is 1 and R19is hydrogen.

[0037] After contacting with the alkylene oxide, a product mixture is provided, wherein the product mixture comprises the bifunctional poly(arylene ether) comprising an end group, wherein the end group comprises a linking group and a terminal functional group, wherein the terminal functional group comprises a hydroxyl group or a salt thereof, and the linking group comprises a substituted or unsubstituted saturated hydrocarbyl group, or a substituted or unsubstituted saturated poly(hydrocarbylene ether) and the polyol. For simplicity, the bifunctional poly(arylene ether) comprising an end group, wherein the end group comprises a linking group and a terminal functional group, wherein the terminal functional group comprises a hydroxyl group or a salt thereof, and the linking group comprises a substituted or unsubstituted saturated hydrocarbyl group, or a substituted or unsubstituted saturated poly(hydrocarbylene ether) can be referred to herein as “the bifunctional poly(arylene ether) comprising the end group”.

[0038] The synthesis of the bifunctional poly (arylene ether) having the end groups can be performed with or without a solvent. Exemplary solvents include aromatic hydrocarbons such as toluene or xylene, or chlorinated aromatic hydrocarbons such as chlorobenzene, o- dichlorobenzene, or 1,2,4-trichlorobenzene, or ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and the like or a combination thereof. For example, the solvent includes toluene. In a preferred aspect, the metal salt of the poly(arylene ether) having phenolic terminal groups is reacted with the alkylene oxide in the absence of solvent. Thus, in an aspect, solvents such as aromatic hydrocarbon solvents (e.g., chlorobenzene, ortho-dichlorobenzene, 1,2,4- trichlorobenzene, toluene, xylene, benzene, and the like) or ketone solvents (e.g., as methyl ethyl ketone, methyl isobutyl ketone, and the like or a combination thereof) can be excluded from the present method. As such, the resulting product mixture obtained by the present method is substantially free of a volatile organic solvent. As used herein, the term “substantially free” means that the mixture includes less than 5 weight percent, or less than 1 weight percent, or less than 0.5 weight percent, or less than 0.1 weight percent, or excludes the recited component.

[0039] A capping catalyst can be employed in the reaction of an uncapped poly(phenylene ether) with a capping agent. Examples of such compounds, including those known to the art, which are capable of catalyzing condensation of phenols with the capping agents described above. For example, the capping catalyst can be a hydroxide salt such as sodium hydroxide, potassium hydroxide, tetraalkylammonium hydroxides, or the like; tertiary alkylamines such as tributyl amine, triethylamine, dimethylbenzylamine, dimethylbutylamine, or the like; tertiary mixed alkyl-arylamines and substituted derivatives thereof such as N,N- dimethylaniline; heterocyclic amines such as imidazoles, pyridines, and substituted derivativesthereof such as 2-methylimidazole, 2-vinylimidazole, 4-(dimethylamino)pyridine, 4-(l- pyrrolino)pyridine, 4-(l-piperidino)pyridine, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, or the like.

[0040] Alternatively, the capping catalyst can be a transesterification catalyst that is capable of catalyzing transesterification of phenols with the capping agents described above can be used. For example, the capping catalyst can be a catalyst that includes a source of alkali or alkaline earth ions. The sources of these ions include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, as well as alkaline earth hydroxides such as magnesium hydroxide and calcium hydroxide. Other sources of alkali and alkaline earth metal ions include the corresponding salts of carboxylic acids (such as sodium acetate) and derivatives of ethylene diamine tetraacetic acid (EDTA) (such as EDTA tetrasodium salt, and EDTA magnesium disodium salt). Other transesterification catalysts include alkali or alkaline earth metal salts of carbonate, such as CS2CO3, NaHCO s. and Na^COi. or the like, non-volatile inorganic acid such as NaFEPCh, NaH2PO4, Na2HPO3, KH2PO4, CSH2PO4, CS2HPO4, or the like, or mixed salts of phosphoric acid, such as NaKHPO4, CsNaHPO4, CSKHPO4, or the like. A combination of the foregoing catalysts can be used.

[0041] The process can further include isolating the bifunctional poly (arylene ether) from the reaction mixture. Suitable methods include precipitation and total isolation methods. A total isolation process can be used for isolating the bifunctional poly(arylene ether) having saturated hydrocarbyl alcohol terminal functional groups when the intrinsic viscosity (I.V.) is less than about 0.25 deciliters per gram (dL / g), as measured in chloroform at 25°C. As part of the total isolation, a portion of the solvent is preferably removed to reduce the solvent load on the total isolation equipment. Concentration of the copolymer containing solution is preferably done by reducing the pressure in a solvent flash vessel while preferably increasing the temperature of the copolymer containing solution. The isolated copolymer can be dried at a temperature that is below the softening temperature or Tgof the capped poly(phenylene ether) copolymer.

[0042] Additionally, conventional methods use the following reagents to incorporate a saturated hydrocarbyl group.wherein R9to R12, R20to R23are each independently hydrogen, C1-12 primary alkyl, C2-12 alkenyl, C7-12 arylalkyl, C2-12 alkoxyalkyl, C7-12 aryloxyalkyl, or C1-12 hydroxyalkyl, preferably hydrogen or C 1-6 alkyl. Another advantage of the poly (arylene ethers) and methods or preparation of the present disclosure is that reagents such as those of Formulas (l)-(3), thus avoiding the formation of side-products. For example, reaction with a reagent of formula (1) results in the formation of a carbonate side product, formula (2) is not widely commercially available and can form elimination products, and reaction with formula (3) results in the formation of an ester side product.

[0043] An example of the end group comprising a carbonate-containing linking group side-product resulting from use of ethylene carbonate is depicted below for illustrative purposes

[0044] An example of the end group comprising an ester-containing linking group sideproduct is depicted below for illustrative purposes only.O o— (CH2)2-O-C - (CH2)2--OHLinking group

[0045] When used in a method of making a thermoplastic polyurethane, such poly(arylene ethers) including terminal carbonate groups, terminal ester groups, or both could be incorporated into the polyurethane. Accordingly, in some aspects, a thermoplastic polyurethane composition including the bifunctional poly(arylene ether) according to the present disclosure minimizes or eliminates the presence of repeating units derived from products other than the bifunctional poly(arylene ether) having the desired end groups. For example, the thermoplastic polyurethane compositions can include 0 to 5,000 ppm of repeating units derived from a poly(arylene ether) a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof.

[0046] In a specific aspect, the bifunctional poly(arylene ether) comprising the end groups from which the arylene ether repeat units of the thermoplastic polyurethane are derived can be made by a method comprising: combining a bifunctional hydroxy-terminatedpoly(arylene ether); and a polyol; to provide a reaction mixture; combining the reaction mixture with a base to provide a basic reaction mixture; removing water from the basic reaction mixture; and combining the basic reaction mixture with a capping agent comprising an alkylene oxide; to provide a product mixture comprising the bifunctional poly(arylene ether) comprising an end group, wherein the end group comprises a linking group and a terminal functional group, wherein the terminal functional group comprises a hydroxyl group or a salt thereof, and the linking group comprises a substituted or unsubstituted saturated hydrocarbylene group, or a substituted or unsubstituted saturated poly(hydrocarbylene ether), wherein the bifunctional poly(arylene ether) comprises an average of at least 1.8 terminal groups or a salt thereof, for example an average of 1.8 to 2 terminal hydroxy groups per molecule.

[0047] The bifunctional poly(arylene ether) comprising an end group, wherein the end group comprises a linking group and a terminal functional group, wherein the terminal functional group comprises a hydroxyl group or a salt thereof, and the linking group comprises a substituted or unsubstituted saturated hydrocarbylene group, or a substituted or unsubstituted saturated poly(hydrocarbylene ether) from which the arylene ether repeat units of the thermoplastic polyurethane are derived can have a number average molecular weight (Mn) of 600 to 10,000, or 600 to 2,500 grams per mole (g / mol) as determined by gel permeation chromatography (GPC) prior to incorporation into the thermoplastic polyurethane. In some aspects, the bifunctional poly (arylene ether) can have a weight average molecular weight (Mw) of 700 to 15,000 g / mol, each as determined by GPC prior to incorporation into the thermoplastic polyurethane. For example, the bifunctional poly( arylene ether) can have a number average molecular weight (Mn) of 600 to 2,200 g / mol or 800 to 1,600 g / mol and a weight average molecular weight (Mw) of 500 to 6,000 g / mol or 800 to 4,500 g / mol, each as determined by GPC prior to incorporation into the thermoplastic polyurethane. For example, the bifunctional poly(arylene ether) can have a number average molecular weight (Mn) of 400 to 2,200 g / mol or 800 to 1,600 g / mol and a weight average molecular weight (Mw) of 600 to 5,000 g / mol or 800 to 4,500 g / mol, each as determined by GPC.

[0048] The bifunctional poly(arylene ether) comprising the end groups from which the arylene ether repeat units of the thermoplastic polyurethane are derived can have an intrinsic viscosity of 0.03 to 0.16 deciliter per gram (dL / g) as measured at 25 °C in chloroform. For example, the intrinsic viscosity is preferably 0.06 to 0.1 dL / g, more preferably 0.075 to 0.090 dL / g, or 0.05 to 0.1 deciliter per gram, or 0.1 to 0.15 deciliter per gram.

[0049] The bifunctional poly(arylene ether) comprising substituted or unsubstituted saturated hydrocarbyl alcohol terminal functional groups from which the arylene ether repeatunits of the thermoplastic polyurethane are derived can have a glass transition temperature of not more than 100 °C, preferably not more than 80 °C as determined according to differential scanning calorimetry (DSC) as per ASTM D3418 with a 20°C / min heating rate.

[0050] The plurality of diisocyanate-derived repeat units can have the structurewherein R9is, independently in each repeat unit, C4-18 hydrocarbylene. The diisocyanate residue repeat units are the residue of the organic diisocyanate reactant, many examples of which are described below. In an aspect, each diisocyanate residue repeat unit independently has a structure selected from

[0051] At least one terminal oxygen atom of each poly(phenylene ether) repeat unit is covalently bonded to a terminal carbamoyl group of a diisocyanate residue repeat unit to form a urethane moiety (-O-C(=O)-NH-). An example of such a urethane linkage between a poly(arylene ether) repeat unit and a diisocyanate residue repeat unit is illustrated by the structure below

[0052] In addition to the poly(arylene ether) repeats units and the diisocyanate residue repeat units, the thermoplastic polyurethane can, optionally, further comprise a plurality of diol repeat units. The diol repeat units are distinct from the poly(arylene ether) repeats units. Each diol repeat unit can be the residue of an alkylene diol, an alkylene ether diol, a polyether diol, an alkoxylate of an aromatic diol, or a polyester diol.

[0053] Examples of alkylene diols include 1 ,2-ethandiol (ethylene glycol),1.2-propanediol (propylene glycol), 1,4-butanediol, 2-ethyl-l,3-hexanediol , 1,3-butanediol, 2- butyl-2-ethyl-l,3-propanediol, 2,4-diethyl-l,5-pentanediol, ethylene glycol, 1,3 -propanediol,2.3-butanediol, 1,5-pentanediol, 1 ,6-hexanediol, 2,2,4-trimethyl-l,3-pentanediol, or a combination thereof.

[0054] Examples of alkylene ether diols include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, dibutylene glycol, tributylene glycol, tetrabutylene glycol, or a combination thereof.

[0055] Examples of polyether diols include polyethylene ether diols, polypropylene ether diols, polybutylene glycols, poly tetramethylene ether diols, ethylene oxide capped polypropylene oxides, or a combination thereof.

[0056] Examples of alkoxylates of aromatic diols include ethoxylated and propoxylated derivatives of hydroquinone, resorcinol, catechol, l,l-bis(3,5-dimethyl-4-hydroxyphenyl)ethane, 1 , 1 -bis(3-chloro-4-hydroxyphenyl)ethane, 1 , 1 -bis(3-methyl-4-hydroxyphenyl)-ethane, 1 ,2-bis(4- hydroxy-3,5-dimethylphenyl)- 1 ,2-diphenylethane, 1 ,2-bis(3-methyl-4-hydroxyphenyl)- 1 ,2- diphenylethane, l,2-bis(3-methyl-4-hydroxyphenyl)ethane, 2,2’-binaphthol, 2,2’-biphenol, 2,2’ - dihydroxy-4,4’ -dimethoxybenzophenone, 2,2’-dihydroxy-4-methoxybenzophenone, 2,2’-dihydroxybenzophenone, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-bromo- 4-hydroxyphenyl)propane, 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4- hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, l,l-bis(3,5-dimethyl- 4-hydroxyphenyl)- 1 -phenylethane, 1 , 1 -bis(3-chloro-4-hydroxyphenyl)- 1 -phenylethane, 1,1- bis(3-methyl-4-hydroxyphenyl)-l-phenylethane, 2,2-bis(4-hydroxy-3,5-dimethyl phenyl)-l- phenylpropane, 2,2-bis(4-hydroxy-3,5-dimethyl phenyl)hexane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)pentane, 2,2-bis(3-methyl-4-hydroxynaphthyl)propane, 2,2-bis(3-methyl-4- hydroxyphenyl)- 1 -phenylpropane, 2,2-bis(3-methyl-4-hydroxyphenyl)hexane, 2,2-bis(3-methyl- 4-hydroxyphenyl)pentane, 2,2'-methylenebis(4-methylphenol), 2,2'-methylenebis[4-methyl-6-(l- methylcyclohexyl)phenol] , 3 ,3 ’ ,5 ,5 ’ -tetramethyl-4, 4’ -biphenol, 3,3’ -dimethyl-4,4’ -biphenol, bis(2-hydroxyphenyl)-methane, bis(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)methane, bis(3,5- dimethyl-4-hydroxyphenyl)methane, bis(3-methyl-4-hydroxyphenyl)methane, bis-(4-hydroxy- 3,5-dimethyl phenyl)cyclohexylmethane, bis(4-hydroxy-3,5-dimethyl phenyl)phenylmethane, bis(3-methyl-4-hydroxyphenyl)cyclohexylmethane, bis(3-methyl-4-hydroxyphenyl)methane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, bis(3-methyl-4-hydroxyphenyl)phenylmethane, 2,2’,3,3’,5,5’-hexamethyl-4,4’-biphenol, octafluoro-4, 4’ -biphenol, 2,3,3’,5,5’-pentamethyl-4,4’- biphenol, 1 , 1 -bis(3,5-dibromo-4-hydroxyphenyl)cyclohexane 1 , 1 -bis(3,5-dimethyl-4- hydroxyphenyl)cyclohexane, bis(3-methyl-4-hydroxyphenyl)cyclohexane, tetrabromobiphenol, tetrabromobisphenol A, tetrabromobisphenol S, 2,2’-diallyl-4,4’-bisphenol A, 2,2’-diallyl-4,4’- bisphenol S, 3,3’,5,5’-tetramethyl-4,4’-bisphenol sulfide, 3,3’-dimethyl bisphenol sulfide, and 3 , 3 ’ ,5 ,5 ’ -tetramethyl-4, 4 ’ -bisphenol sulfone.

[0057] Examples of polyester diols include aliphatic polyester diols (sometimes called aliphatic polyester polyols), aromatic polyester diols (sometimes called aromatic polyester polyols), and polycaprolactone diols. It will be understood that aromatic polyester diols include aromatic repeat units and can, optionally, further include aliphatic repeat units, as in poly (ethylene terephthalate) and poly (butylene terephthalate).

[0058] Since unreacted groups at the end of the polymer chain can undergo additional reactions during melt processing the thermoplastics polyurethane, a monohydric phenol or a monohydric alcohol or a monoisocyanate can be used to end-cap the polymer to control molecular weight and give more stable material.

[0059] The weight percent of poly(phenylene ether) repeat units and diisocyanate residue repeat units in the thermoplastic polyurethane will depend on the molecular weights of the hydroxy-diterminated poly(phenylene ether) and the organic diisocyanate from which the thermoplastic polyurethane is formed. In general, the thermoplastic polyurethane will comprise 5 to 95 weight percent of the poly(phenylene ether) repeat units, and 5 to 40 weight percent of the diisocyanate residue repeat units, based on the weight of the thermoplastic polyurethane. The thermoplastic polyurethane can, optionally, further comprise 5 to 70 weight percent of diol repeat units, each diol repeat unit comprising the residue of an alkylene diol, an alkylene ether diol, a polyether diol, an alkoxylate of an aromatic diol, or a polyester diol.

[0060] In an aspect, the thermoplastic polyurethane can have a weight average molecular weight of 10,000 to 250,000 grams per mole (g / mole), specifically 50,000 to 250,000 g / mole.

[0061] The thermoplastic polyurethane composition can advantageously exhibit improved dielectric properties. For example, in an aspect, the thermoplastic polyurethane composition can exhibit a dielectric constant of less than 5.0 at 1 MHz according to ASTM DI 50, a dissipation factor of less than 0.025 at 1 MHz according to ASTM DI 50, or both.

[0062] The present disclosure includes articles formed from the thermoplastic polyurethane composition. Suitable methods of forming such articles include single layer and multilayer sheet extrusion, injection molding, blow molding, film extrusion, profile extrusion, pultrusion, compression molding, thermoforming, pressure forming, hydroforming, vacuum forming, and the like. A combination of the foregoing article fabrication methods can be used. In an aspect, the article is formed by injection molding or profile extrusion. Examples of articles that can be formed by extrusion include cable sheathing, spiral tubing, pneumatic tubing, blow molded bellows, and films. Examples of articles that can be formed by injection molding include ski boot shells, sport shoe soles, caster tires, automotive body panels, and automotive rocker panels.

[0063] Another aspect of the present disclosure is a method of forming a thermoplastic polyurethane composition. The method comprises reacting a bifunctional poly(arylene ether) comprising substituted or unsubstituted saturated hydrocarbylene alcohol terminal functional groups with an organic diisocyanate to form a thermoplastic polyurethane.

[0064] The bifunctional poly(arylene ether) comprising the end groups can have the structurewherein each occurrence of Q1Q2, Rl, R2, R3, R4, x, y, and Y is as defined above in reference to the arylene ether repeat units.

[0065] All of the structural variations described above for the poly (arylene ether) repeat units apply as well to the bifunctional poly (arylene ether) s from which they are derived. Methods of preparing bifunctional poly(arylene etherjs are discussed above.

[0066] In an aspect the bifunctional poly(arylene ether) can be made by a method comprising combining a bifunctional hydroxy-terminated poly(arylene ether); and a polyol; toprovide a reaction mixture; combining the reaction mixture with a base to provide a basic reaction mixture; removing water from the basic reaction mixture; and combining the basic reaction mixture with a capping agent comprising an alkylene oxide; to provide a product mixture comprising the bifunctional poly( arylene ether) comprising an end group, wherein the end group comprises a linking group and a terminal functional group, wherein the terminal functional group comprises a hydroxyl group or a salt thereof, and the linking group comprises a substituted or unsubstituted saturated hydrocarbylene group, or a substituted or unsubstituted saturated poly(hydrocarbylene ether) and the polyol, wherein the bifunctional poly(arylene ether) comprises an average of at least 1.8 alcohol terminal functional groups or a salt thereof.

[0067] Polyols can include polyether polyols prepared by reacting an initiator having 2 to 8 hydroxyl groups per molecule, specifically 3 to 8 hydroxyl groups per molecule, with an alkoxylating agent such as ethylene oxide, propylene oxide, or butylene oxide. Exemplary polyols include an ethoxylated saccharide, a propoxylated saccharide, a butoxylated saccharide, an ethoxylated glycerin, a propoxylated glycerin, a butoxylated glycerin, an ethoxylated diethanolamine, a propoxylated diethanolamine, a butoxylated diethanolamine, an ethoxylated triethanolamine, a propoxylated triethanolamine, a butoxylated triethanolamine, an ethoxylated trimethylolpropane, a propoxylated trimethylolpropane, a butoxylated trimethylolpropane, an ethoxylated erythritol, a propoxylated erythritol, a butoxylated erythritol, an ethoxylated pentaerythritol, a propoxylated pentaerythritol, a butoxylated pentaerythritol, an aliphatic polyester diol, an aromatic polyester polyol, polyethylene glycol, polypropylene glycol, poly(tetramethylene glycol), butanediol, hexanediol, other C2-8 glycols, or a combination thereof.

[0068] In a specific aspect, the polyol is a polyether polyol comprising poly (tetramethylene glycol). The poly (tetramethylene glycol) can generally be of any molecular weight. For example, the poly(tetramethylene glycol) can have a number average molecular weight of 500 to 5000 grams per mole (g / mole). Within this range, the poly(tetramethylene glycol) can have a number average molecular weight of 500 to 4000 g / mol, or 500 to 3000 g / mole, or 500 to 2500 g / mole, or 650 to 1250 g / mole.

[0069] The bifunctional hydroxy-terminated poly(arylene ether) and the polyol are combined to provide a reaction mixture. The bifunctional hydroxy-terminated poly(arylene ether) can be present in the reaction mixture in an amount of 20 to 60 weight percent, or 30 to 50 weight percent, or 35 to 45 weight percent, each based on the total weight of the reaction mixture.

[0070] The reaction mixture in turn combined with a base to provide a basic reaction mixture. Suitable bases can include, for example alkali metal hydroxides (e.g., lithium hydroxide, sodium hydroxide, and potassium hydroxide), alkaline earth hydroxides (e.g., magnesium hydroxide and calcium hydroxide), non-nucleophilic bases (e.g., amines such as triethyl amine), alkali metal hydrides (e.g., lithium hydride, sodium hydride, and potassium hydride), and alkali metal carbonates (e.g., sodium carbonate or sodium bicarbonate). In a preferred aspect, the base includes sodium hydroxide or potassium hydroxide, more preferably potassium hydroxide. Both phenolic OH groups are converted to a phenoxide salt when combined with the base.

[0071] The base can be added in an amount of 1 to 10 mole percent, based on the total moles of the bifunctional poly(arylene ether) hydroxyl groups. Within this range, the base can be added in an amount of 2 to 7 mole percent, or 4 to 6 mole percent, each based on the total moles of the bifunctional poly (arylene ether) hydroxyl groups.

[0072] The method further comprises removing water from the basic reaction mixture. Removing water from the basic reaction mixture can generally be by any means effective to reduce the concentration of water in the basic reaction mixture, preferably to a concentration of 100 parts per million (ppm) or less. In an aspect, removing the water can comprise passing dry nitrogen through the basic reaction mixture for a time sufficient to reduce the moisture content to 100 ppm or less.

[0073] Following reduction in water content to a level of 100 ppm or less, the dried basic reaction mixture is combined with a capping agent comprising an alkylene oxide. The alkylene oxide can be of the formulawherein p is 1-3, preferably 1-2 and R19is hydrogen or Ci-is primary alkyl, preferably hydrogen or Ci-6 alkyl, more preferably hydrogen or C1-3 alkyl. In some aspects, p is 1-3, R19is hydrogen or methyl, preferably p is 1-2 and R19is hydrogen, more preferably p is 1 and R19is hydrogen.

[0074] In a specific aspect, the capping agent comprises an epoxide according to the formulawherein R19is hydrogen or a substituted or unsubstituted Ci-is alkyl group. In an aspect, the capping agent can comprise ethylene oxide, propylene oxide, or a combination thereof. In a specific aspect, the capping agent can comprise ethylene oxide.

[0075] The alkylene oxide is combined with the dried basic reaction mixture in an amount effective to provide a molar ratio of alkylene oxide:poly(arylene ether) hydroxyl groups of 0.01:1 to 1:1, or 0.01:1 to 0.1:1, or 0.02:1 to 0.07:1.

[0076] After contacting with the alkylene oxide, a product mixture is provided, wherein the product mixture comprises the bifunctional poly(arylene ether) comprising substituted or unsubstituted saturated hydrocarbylene alcohol terminal functional groups or a salt thereof and the polyol.

[0077] Optionally, the product mixture can be directly reacted with the organic diisocyanate to form the thermoplastic polyurethane.

[0078] The organic diisocyanate can the structureO=C=N - R9— N=C=O wherein R9is C4-18 hydrocarbylene.

[0079] Examples of organic diisocyanates that can be used in the reaction include 1 ,4-tetramethylene diisocyanate, 1 ,6-hexamethylene diisocyanate, 2,2,4-trimethyl-l,6- hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane- 1,3-diisocyanate, and cyclohexane- 1 ,4-diisocyanate, l-isocyanato-2-isocyanatomethyl cyclopentane, l-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (isophorone diisocyanate or IPDI), bis(4-isocyanatocyclohexyl)methane, 2,4'-dicyclohexyl-methane diisocyanate, 1 ,3-bis(isocyanatomethyl)-cyclohexane, 1 ,4-bis-(isocyanatomethyl)-cyclohexane, bis(4- isocyanato-3-methyl-cyclohexyl)methane, alpha, alpha, alpha’ , alpha’ -tetramethyl- 1 ,3-xylylene diisocyanate, alpha, alpha, alpha’, alpha’ -tetramethyl- 1,4-xylylene diisocyanate, 1-isocyanato-l- methyl-4(3)-isocyanatomethyl cyclohexane, 2,4-hexahydrotoluene diisocyanate, 2,6- hexahydrotoluene diisocyanate, 1,3-phenylene diisocyanate, 1 ,4-phenylene diisocyanate, 2,4- toluene diisocyanate, 2,6-toluene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4’- diphenylmethane diisocyanate, 1 ,5-diisocyanato naphthalene, and mixtures thereof. In some aspects, the diisocyanate comprises 1 ,6-hexamethylene diisocyanate, l-isocyanato-3- isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate or IPDI), bis-(4- isocyanatocyclohexyl)me thane, alpha, alpha, alph’ , alpha’ -tetramethyl- 1 ,3-xylylene diisocyanate, alpha, alpha, alph’ , alpha’ -tetramethyl- 1 ,4-xylylene diisocyanate, 1 -isocyanato- 1 -methyl-4(3)- isocyanatomethyl cyclohexane, 2,4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluylene diisocyanate, 2,4-diphenylmethanediisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3-dimethyl-4,4-biphenyldiisocyanate, naphthalene-l,5-diisocyanate, l-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcylohexane, polyphenylene diisocyanate, or a mixture thereof.

[0080] As described above, the organic diisocyanate can be reacted with a diol in addition to the hydroxy-diterminated poly(phenylene ether). The diol is selected from alkylene diols, alkylene ether diols, polyether diols, alkoxylates of aromatic diols, polyester diols, or a combination thereof.

[0081] The organic diisocyanate can, optionally, be reacted with a diamine in addition to the hydroxy-diterminated poly(phenylene ether). Specific diamines include, for example, toluenediamines , dimethylthiotoulenediamines , 3,5 -diethyltoluene-2 ,4-diamine, 3,5-diethyltoluene-2,6-diamine, methylenebis(2,6-diethylaniline), or a combination thereof. When a diamine is employed, the product polyurethane comprises repeating units in which each amine group has reacted with an isocyanate group to form a urea moiety.

[0082] Reacting the organic diisocyanate with the hydroxy-diterminated poly(phenylene ether) and, optionally, the diol, yields a linear thermoplastic polyurethane. If a branched or crosslinked polyurethane is desired, a poly(phenylene ether) having more than two hydroxy groups and / or an isocyanate compound having more than two isocyanate groups and / or a polyol having at least three hydroxyl groups can be employed.

[0083] A catalyst can be used, or the reaction can proceed in the absence of a catalyst. When present, suitable catalysts include tertiary amines and metal compounds based on tin, bismuth, and zinc. Tertiary amine catalysts include triethylenediamine (TEDA, 1,4- diazabicyclo[2.2.2]octane or DABCO), dimethylcyclohexylamine (DMCHA), dimethylethanolamine (DMEA), and N-ethylmorpholine. Specific metal compounds include bismuth and zinc carboxylates, organotin compounds (including dibutyltin dilaurate and tin carboxylates such as stannous octoate), oxides of tin, bismuth and zinc, and mercaptides of tin, bismuth, and zinc.

[0084] A solvent can be present during the reaction, or the reaction can proceed without a solvent.

[0085] This disclosure is further illustrated by the following examples, which are nonlimiting.EXAMPLES

[0086] Materials used in the following examples are described in Table 1.Table 1Preparative Example 1.

[0087] PPE-OH-2 was prepared according to the following general procedure. A 50 wt% solution of poly(phenylene ether) oligomer was prepared by dissolving 1kg of poly(phenylene ether) oligomer in 1.1 kg of MIBK (methyl isobutyl ketone) at 60 °C with stirring. To this solution was added 2 mol% of KOH (39.2g of a 50 wt% solution in water) and the solution dried by pulling a slight vacuum and distilling out ~100g of the solvent (until it ran clear.) This solution was then transferred under N2 into a 4L autoclave and ethylene oxide (4.5g, gas) was transferred into it. The autoclave was heated to 135 °C and held until the pressure drop stopped and was stable. The reactor was cooled to 25 °C and the solution discharged. The resin was collected by precipitation with 5 equivalents of methanol, filtered and dried in a 100 °C vacuum oven overnight.

[0088] Dielectric constant (Dk) and dissipation factor (Df) were determined on a QWED split post dielectric resonator and Agilent PNA network analyzer. Dielectric properties (dielectric constant (Dk) and dissipation factor (Df)) were measured using a parallel plate methodology. Specifically, the IPC-TM-650 2.5.5.9 test standard was applied to determine Dk and Df in the frequency range from 100 MHz to 1 GHz. A Keysight E4991B impedance analyzer coupled to an H-P 16453 A dielectric material test fixture were the equipment used for dielectric characterization.

[0089] Test samples were conditioned in a room temperature environment with 50% relative humidity for > 24 hours prior to measurement. Thickness was determined with the use of a Filetta digital micrometer with 0.001 mm resolution.

[0090] Polyurethanes were prepared from the reactants described in Table 2.

[0091] Cast polyurethanes were provided by the prepolymer method. In a typical procedure for cast elastomer preparation, a calculated amount of prepolymer is weighed into a 100g cup (suited for SpeedMixer) and heated in an oven at 70°C for one hour. Calculated amount of a curing agent (such as Ethacure 300) is added to the prepolymer and mixed by aSpeedMixerTM (FlackTek Inc.) for one minute. At the gel time, the mixture is transferred to an aluminum mold covered with a Teflon sheet, which is pre-heated to 70°C. When gelation occurs, as determined by string formation, the mold is placed in the hydraulic press and the resin compression-molded at about 20,000 psi for 60 minutes.

[0092] Thermoplastic polyurethanes were prepared by the quasi-prepolymer method. For example, NCO-terminated quasi-prepolymers based on 4,4 ’-MDI and polyol (PPG 1000 or the blends with PPE polyol) were prepared by reacting calculated amount of isocyanate and polyol (as required for targeted NCO%) using the following procedure: 4,4’ -MDI liquified and conditioned at 50°C was weighed in a cup suited for Speed Mixer and conditioned at 50°C. The polyol, conditioned at 50°C, was added to the cup with isocyanate and mixed in Speed Mixer for 60 seconds. The cup was purged with nitrogen, closed, and placed in an oven at 50°C for at least 16 hours to complete reaction. Benzoyl chloride (inhibitor of isocyanate reactivity) was added to polyol blend(s) containing PPE polyol(s) prior to reaction with isocyanate in quazi-prepolymer synthesis The NCO% of the quazi-prepolymer was determined according to ASTM D 5155-01.

[0093] The polyurethanes were evaluated for dielectric constant (Dk) and dissipation factor (Df). Amounts of each component used to prepare the polymer compositions are provided in Table 2 in grams. Properties are also shown in Table 2.Table 2

[0094] As shown in Table 2, incorporation of the hydroxyalkyl functionalized poly(phenylene ether) into the polyurethane structure reduced the dielectric constant and the dissipation factor.

[0095] This disclosure further encompasses the following aspects.

[0096] Aspect 1 : A thermoplastic polyurethane composition comprising a thermoplastic polyurethane copolymer comprising a plurality of arylene ether repeat units derived from a bifunctional poly(arylene ether) comprising an end group, wherein the end group comprises alinking group and a terminal functional group, wherein the terminal functional group comprises a hydroxyl group or a salt thereof, and the linking group comprises a substituted or unsubstituted saturated hydrocarbylene group, or a substituted or unsubstituted saturated poly(hydrocarbylene ether); and a plurality of diisocyanate-derived repeat units; wherein at least one terminal oxygen atom of each arylene ether repeat unit is covalently bonded to a terminal carbamoyl group of a diisocyanate-derived repeat unit to form a urethane moiety; and wherein the composition comprises 0 to 5,000 ppm of a poly(arylene ether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof.

[0097] Aspect 2: The thermoplastic polyurethane composition of aspect 1, wherein the plurality of arylene ether repeat units have the structurewherein each occurrence of Q1is independently halogen, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; each occurrence of Q2is independently hydrogen, halogen, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; each occurrence of R1and R2is independently hydrogen, halogen, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; each occurrence of R3and R4is independently hydrogen, halogen, or C1-18 alkyl; m and n are independently 0 to 20, provided that the sum of m and n is at least 3; x is independently at each occurrence 0 to 40, provided that at least one occurrence of x is 1 ; y is independently at each occurrence at least 1, preferably 1 to 3; and Y iswherein each occurrence of Ra, Rb, Rc, Rd, and Reis independently hydrogen, C1-12 hydrocarbyl, or Ci -6 hydrocarbylene, optionally wherein Raand Rbor Rcand Rdtogether are a C4-8 alkylene group; each occurrence of R7is independently hydrogen, a C1-14 hydrocarbyl, a C1-14 halohydrocarbyl, or a C1-14 heterohydrocarbyl, preferably C1-13 alkyl, C1-13 alkoxy, C2-13 alkenyl, C2-13 alkenyloxy, C3-6 cycloalkyl, C3-6 cycloalkoxy, Ce-14 aryl, Ce-io aryloxy, C7-13 arylalkyl, C7-13 arylalkoxy, C7-13 alkylaryl, or C7-13 alkylaryloxy; each occurrence of R8is independently a C1-6 hydrocarbylene group, preferably a divalent C2-8 aliphatic group, more preferably dimethylene, trimethylene, or tetramethylene; and E is 2 to 200, 2 to 125, 5 to 125, 5 to 100, 5 to 50, 20 to 80, 10 to 60, or 5 to 20; and wherein the plurality of diisocyanate-derived repeat units have the structurewherein R9is, independently in each repeat unit, C4-18 hydrocarbylene.

[0098] Aspect 3: The thermoplastic polyurethane of aspect 1 or 2, wherein the arylene ether repeat units have the structurewherein x is independently at each occurrence 0 to 15, preferably 0 to 1, provided that at least one occurrence of x is 1.

[0099] Aspect 4: The thermoplastic polyurethane of any of aspects 1 to 3, wherein each diisocyanate-derived repeat unit independently has a structure selected from

[0100] Aspect 5: The thermoplastic polyurethane of any of aspects 1 to 4, further comprising a plurality of diol repeat units, each diol repeat unit comprising the residue of an alkylene diol, an alkylene ether diol, a polyether diol, an alkoxylate of an aromatic diol, or a polyester diol.

[0101] Aspect 6: The thermoplastic polyurethane of any of aspects 1 to 5, comprising: 5 to 95 weight percent of the arylene ether repeat units, and 5 to 95 weight percent of the diisocyanate residue repeat units.

[0102] Aspect 7: The thermoplastic polyurethane of aspect 6, further comprising 5 to 70 weight percent of diol repeat units, each diol repeat unit comprising the residue of an alkylene diol, an alkylene ether diol, a polyether diol, an alkoxylate of an aromatic diol, or a polyester diol.

[0103] Aspect 8: The thermoplastic polyurethane of any of aspects 1 to 7, having a weight average molecular weight of 10,000 to 250,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards.

[0104] Aspect 9: The thermoplastic polyurethane of any of aspects 1 to 8, wherein the bifunctional poly(arylene ether) comprising substituted or unsubstituted saturatedhydrocarbylene alcohol terminal functional groups is made by a method comprising: combining a bifunctional hydroxy-terminated poly(arylene ether); and a polyol; to provide a reaction mixture; combining the reaction mixture with a base to provide a basic reaction mixture; removing water from the basic reaction mixture; and combining the basic reaction mixture with a capping agent comprising an alkylene oxide; to provide a product mixture comprising the bifunctional poly(arylene ether) comprising substituted or unsubstituted saturated hydrocarbylene alcohol terminal functional groups or a salt thereof and the polyol, wherein the bifunctional poly(arylene ether) comprises an average of at least 1.8 terminal substituted or unsubstituted saturated hydrocarbylene alcohol terminal functional groups or a salt thereof.

[0105] Aspect 10: The thermoplastic polyurethane of any of aspects 1 to 9, wherein the thermoplastic polyurethane exhibits a dielectric constant of less than 5.0 at 1 MHz according to ASTM D150; and a dissipation factor of less than 0.025 at 1 MHz according to ASTM D150.

[0106] Aspect 11: An article comprising the thermoplastic polyurethane composition of any of aspects 1 to 10.

[0107] Aspect 12: The article of aspect 11, wherein the article is a coating, a film, cable sheathing, spiral tubing, pneumatic tubing, blow molded bellows, ski boot shells, sport shoe soles, caster tires, automotive body panels, and automotive rocker panels.

[0108] Aspect 13: A method of forming a thermoplastic polyurethane, the method comprising: reacting a bifunctional poly(arylene ether) comprising an end group, wherein the end group comprises a linking group and a terminal functional group, wherein the terminal functional group comprises a hydroxyl group or a salt thereof, and the linking group comprises a substituted or unsubstituted saturated hydrocarbylene group, or a substituted or unsubstituted saturated poly(hydrocarbylene ether) with an organic diisocyanate to form a thermoplastic polyurethane; preferably wherein the bifunctional poly(arylene ether) has the structurewherein each occurrence of Q1is independently halogen, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; each occurrence of Q2is independently hydrogen, halogen, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, C2-12 halohydrocarbyloxy wherein at leasttwo carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; each occurrence of R1and R2is independently hydrogen, halogen, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; each occurrence of R3and R4is independently hydrogen, halogen, or C1-18 alkyl; m and n are independently 0 to 20, provided that the sum of m and n is at least 3; x is independently at each occurrence 0 to 40, provided that at least one occurrence of x is 1 ; y is independently at each occurrence at least 1, preferably 1 to 3; and Y iswherein each occurrence of Ra, Rb, Rc, Rd, and Reis independently hydrogen, C1-12 hydrocarbyl, or Ci -6 hydrocarbylene, optionally wherein Raand Rbor Rcand Rdtogether are a C4-8 alkylene group; each occurrence of R7is independently hydrogen, a C1-14 hydrocarbyl, a C1-14 halohydrocarbyl, or a C1-14 heterohydrocarbyl, preferably C1-13 alkyl, C1-13 alkoxy, C2-13 alkenyl, C2-13 alkenyloxy, C3-6 cycloalkyl, C3-6 cycloalkoxy, Ce-i4 aryl, Ce-io aryloxy, C7-13 arylalkyl, C7-13 arylalkoxy, C7-13 alkylaryl, or C7-13 alkylaryloxy; each occurrence of R8is independently a C1-6 hydrocarbylene group, preferably a divalent C2-8 aliphatic group, more preferably dimethylene, trimethylene, or tetramethylene; and E is 2 to 200, 2 to 125, 5 to 125, 5 to 100, 5 to 50, 20 to 80, 10 to 60, or 5 to 20; and wherein the organic diisocyanate has the structureO=C=N - R9— N=C=O wherein R9is C4-18 hydrocarbylene.

[0109] Aspect 14: The method of aspect 13, further comprising: forming the bifunctional poly(arylene ether) comprising substituted or unsubstituted saturated hydrocarbylene alcohol terminal functional groups according to a method comprising: combining a bifunctional hydroxy-terminated poly (arylene ether); and a polyol; to provide a product mixture comprising the bifunctional poly(arylene ether) comprising the end group, wherein the bifunctional poly(arylene ether) comprises an average of at least 1.8 terminal substituted or unsubstituted saturated hydrocarbylene alcohol terminal functional groups or a salt thereof, preferably wherein the product mixture comprises 0 to 5,000 ppm of a poly (aryleneether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof; and directly reacting the product mixture with the organic diisocyanate to form the thermoplastic polyurethane.

[0110] Aspect 15: The method of aspect 13 or 14, wherein the reacting the bifunctional poly(arylene ether) with the organic diisocyanate is by reactive extrusion.

[0111] The compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed. The compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any materials (or species), steps, or components, that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.

[0112] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. “Combination” is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms “first,” “second,” and the like, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms “a” and “an” and “the” do not denote a limitation of quantity, and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. “Or” means “and / or” unless clearly stated otherwise. Reference throughout the specification to “an aspect” means that a particular element described in connection with the aspect is included in at least one aspect described herein, and may or may not be present in other aspects. The term “combination thereof’ as used herein includes one or more of the listed elements, and is open, allowing the presence of one or more like elements not named. In addition, it is to be understood that the described elements can be combined in any suitable manner in the various aspects.

[0113] Unless specified to the contrary herein, all test standards are the most recent standard in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears.

[0114] Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this application belongs. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.

[0115] Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valency filled by a bond as indicated, or a hydrogen atom. A dashthat is not between two letters or symbols is used to indicate a point of attachment for a substituent. For example, -CHO is attached through carbon of the carbonyl group.

[0116] As used herein, the term “hydrocarbyl”, whether used by itself, or as a prefix, suffix, or fragment of another term, refers to a residue that contains only carbon and hydrogen. The residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain a combination of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. However, when the hydrocarbyl residue is described as substituted, it can optionally contain heteroatoms over and above the carbon and hydrogen members of the substituent residue. Thus, when specifically described as substituted, the hydrocarbyl residue can also contain one or more carbonyl groups, amino groups, hydroxyl groups, or the like, or it can contain heteroatoms within the backbone of the hydrocarbyl residue. The term "alkyl" means a branched or straight chain, saturated aliphatic hydrocarbon group, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s- pentyl, and n- and s-hexyl. “Alkenyl” means a straight or branched chain, monovalent hydrocarbon group having at least one carbon-carbon double bond (e.g., ethenyl (-HC=CH2)). “Alkoxy” means an alkyl group that is linked via an oxygen (i.e., alkyl-O-), for example methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH2-) or, propylene (-(CH2)3- )). “Cycloalkylene” means a divalent cyclic alkylene group, -CnH2n-x, wherein x is the number of hydrogens replaced by cyclization(s). “Cycloalkenyl” means a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl. “Arylene” means a divalent aryl group. “Alkylarylene” means an arylene group substituted with an alkyl group. “Arylalkylene” means an alkylene group substituted with an aryl group (e.g., benzyl). The prefix "halo" means a group or compound including one more of a fluoro, chloro, bromo, or iodo substituent. A combination of different halo atoms (e.g., bromo and fluoro), or only chloro atoms can be present. The prefix “hetero” means that the compound or group includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein the heteroatom(s) is each independently N, O, S, Si, or P. “Substituted” means that the compound or group is substituted with at least one (e.g., 1, 2, 3, or 4) substituents that can eachindependently be a C1-9 alkoxy, a C1-9 haloalkoxy, a nitro (-NO2), a cyano (-CN), a C1-6 alkyl sulfonyl (-S(=O)2-alkyl), a C6-12 aryl sulfonyl (-S(=O)2-aryl), a thiol (-SH), a thiocyano (-SCN), a tosyl (CH3C6H4SO2-), a C3-12 cycloalkyl, a C2-12 alkenyl, a C5-12 cycloalkenyl, a C6-12 aryl, a C7- 13 arylalkylene, a C4-12 heterocycloalkyl, and a C3-12 heteroaryl instead of hydrogen, provided that the substituted atom’s normal valence is not exceeded. The number of carbon atoms indicated in a group is exclusive of any substituents. For example -CH2CH2CN is a C2 alkyl group substituted with a nitrile.

[0117] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.

Claims

CLAIMSWhat is claimed is:

1. A thermoplastic polyurethane composition comprising a thermoplastic polyurethane copolymer comprising a plurality of arylene ether repeat units derived from a bifunctional poly(arylene ether) comprising an end group, wherein the end group comprises a linking group comprising a substituted or unsubstituted saturated hydrocarbylene group or a substituted or unsubstituted saturated poly(hydrocarbylene ether), and a terminal functional group comprising a hydroxyl group or a salt thereof, and a plurality of diisocyanate-derived repeat units; wherein at least one terminal oxygen atom of each arylene ether repeat unit is covalently bonded to a terminal carbamoyl group of a diisocyanate-derived repeat unit to form a urethane moiety; and wherein the composition comprises 0 to 5,000 ppm of a poly (arylene ether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof.

2. The thermoplastic polyurethane composition of claim 1, wherein the plurality of arylene ether repeat units have the structurewherein each occurrence of Q1is independently halogen, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; each occurrence of Q2is independently hydrogen, halogen, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; each occurrence of R1and R2is independently hydrogen, halogen, C1-12 hydrocarbylthio,C1-12 hydrocarbyloxy, C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; each occurrence of R3and R4is independently hydrogen, halogen, or Ci-is alkyl; m and n are independently 0 to 20, provided that the sum of m and n is at least 3; x is independently at each occurrence 0 to 40, provided that at least one occurrence of x is 1; y is independently at each occurrence at least 1, preferably 1 to 3; andY iswherein each occurrence of Ra, Rb, Rc, Rd, and Reis independently hydrogen, C1-12 hydrocarbyl, or Ci -6 hydrocarbylene, optionally wherein Raand Rbor Rcand Rdtogether are a C4-8 alkylene group; each occurrence of R7is independently hydrogen, a C1-14 hydrocarbyl, a C1-14 halohydrocarbyl, or a C1-14 heterohydrocarbyl, preferably C1-13 alkyl, C1-13 alkoxy, C2-13 alkenyl, C2-13 alkenyloxy, C3-6 cycloalkyl, C3-6 cycloalkoxy, Ce-14 aryl, Ce-io aryloxy, C7-13 arylalkyl, C7-13 arylalkoxy, C7-13 alkylaryl, or C7-13 alkylaryloxy; each occurrence of R8is independently a C1-6 hydrocarbylene group, preferably a divalent C2-8 aliphatic group, more preferably dimethylene, trimethylene, or tetramethylene; and E is 2 to 200, 2 to 125, 5 to 125, 5 to 100, 5 to 50, 20 to 80, 10 to 60, or 5 to 20; and wherein the plurality of diisocyanate-derived repeat units have the structurewherein R9is, independently in each repeat unit, C4-18 hydrocarbylene.

3. The thermoplastic polyurethane composition of claim 1 or 2, wherein the arylene ether repeat units have the structurewherein x is independently at each occurrence 0 to 15, preferably 0 to 1, provided that at least one occurrence of x is 1.

4. The thermoplastic polyurethane composition of any of claims 1 to 3, wherein each diisocyanate-derived repeat unit independently has a structure selected from5. The thermoplastic polyurethane composition of any of claims 1 to 4, further comprising a plurality of diol repeat units, each diol repeat unit comprising the residue of an alkylene diol, an alkylene ether diol, a polyether diol, an alkoxylate of an aromatic diol, or a polyester diol.

6. The thermoplastic polyurethane composition of any of claims 1 to 5, comprising:5 to 95 weight percent of the arylene ether repeat units, and5 to 95 weight percent of the diisocyanate residue repeat units.

7. The thermoplastic polyurethane composition of claim 6, further comprising 5 to 70 weight percent of diol repeat units, each diol repeat unit comprising the residue of an alkylene diol, an alkylene ether diol, a polyether diol, an alkoxylate of an aromatic diol, or a polyester diol.

8. The thermoplastic polyurethane composition of any of claims 1 to 7, having a weight average molecular weight of 10,000 to 250,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards.

9. The thermoplastic polyurethane composition of any of claims 1 to 8, wherein the bifunctional poly (arylene ether) is made by a method comprising: combining a bifunctional hydroxy-terminated poly (arylene ether); and a polyol; to provide a reaction mixture; combining the reaction mixture with a base to provide a basic reaction mixture; removing water from the basic reaction mixture; and combining the basic reaction mixture with a capping agent comprising an alkylene oxide; to provide a product mixture comprising the bifunctional poly(arylene ether) comprising the end group, wherein the bifunctional poly(arylene ether) comprises an average of at least 1.8 terminal substituted or unsubstituted saturated hydrocarbylene alcohol terminal functional groups or a salt thereof, preferably wherein the product mixture comprises 0 to 5,000 ppm of a poly(arylene ether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof.

10. The thermoplastic polyurethane composition of any of claims 1 to 9, wherein the thermoplastic polyurethane composition exhibits a dielectric constant of less than 5.0 at 1 MHz according to ASTM D150; and a dissipation factor of less than 0.025 at 1 MHz according to ASTM D150.

11. An article comprising the thermoplastic polyurethane composition of any of claims 1 to 10.

12. The article of claim 11, wherein the article is a coating, a film, cable sheathing, spiral tubing, pneumatic tubing, blow molded bellows, ski boot shells, sport shoe soles, caster tires, automotive body panels, and automotive rocker panels.

13. A method of forming a thermoplastic polyurethane composition, the method comprising: reacting a bifunctional poly(arylene ether) comprising an end group, wherein the end group comprises a linking group comprises a substituted or unsubstituted saturated hydrocarbylene group or a substituted or unsubstituted saturated poly(hydrocarbylene ether), and a terminal functional group comprising a hydroxyl group or a salt thereof, with an organic diisocyanate to form a thermoplastic polyurethane; wherein the thermoplastic polyurethane composition comprises 0 to 5,000 ppm of repeating units derived from a poly(arylene ether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof; preferably wherein the bifunctional poly(arylene ether) has the structurewherein each occurrence of Q1is independently halogen, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; each occurrence of Q2is independently hydrogen, halogen, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; each occurrence of R1and R2is independently hydrogen, halogen, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; each occurrence of R3and R4is independently hydrogen, halogen, or Ci-is alkyl;m and n are independently 0 to 20, provided that the sum of m and n is at least 3; x is independently at each occurrence 0 to 40, provided that at least one occurrence of x is 1; y is independently at each occurrence at least 1, preferably 1 to 3; andY iswherein each occurrence of Ra, Rb, Rc, Rd, and Reis independently hydrogen, C1-12 hydrocarbyl, or Ci -6 hydrocarbylene, optionally wherein Raand Rbor Rcand Rdtogether are a C4-8 alkylene group; each occurrence of R7is independently hydrogen, a C1-14 hydrocarbyl, a C1-14 halohydrocarbyl, or a C1-14 heterohydrocarbyl, preferably C1-13 alkyl, C1-13 alkoxy, C2-13 alkenyl, C2-13 alkenyloxy, C3-6 cycloalkyl, C3-6 cycloalkoxy, Ce-i4 aryl, Ce-io aryloxy, C7-13 arylalkyl, C7-13 arylalkoxy, C7-13 alkylaryl, or C7-13 alkylaryloxy; each occurrence of R8is independently a C1-6 hydrocarbylene group, preferably a divalent C2-8 aliphatic group, more preferably dimethylene, trimethylene, or tetramethylene; and E is 2 to 200, 2 to 125, 5 to 125, 5 to 100, 5 to 50, 20 to 80, 10 to 60, or 5 to 20; and the organic diisocyanate has the structureO=C=N - R9— N=C=O wherein R9is C4-18 hydrocarbylene.

14. The method of claim 13, further comprising: forming the bifunctional poly (arylene ether) according to a method comprising: combining a bifunctional hydroxy-terminated poly (arylene ether); and a polyol; to provide a reaction mixture; combining the reaction mixture with a base to provide a basic reaction mixture; removing water from the basic reaction mixture; andcombining the basic reaction mixture with a capping agent comprising an alkylene oxide; to provide a product mixture comprising the bifunctional poly(arylene ether) comprising the end group, wherein the bifunctional poly(arylene ether) comprises an average of at least 1.8 terminal substituted or unsubstituted saturated hydrocarbylene alcohol terminal functional groups or a salt thereof, preferably wherein the product mixture comprises 0 to 5,000 ppm of a poly(arylene ether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof; and directly reacting the product mixture with the organic diisocyanate to form the thermoplastic polyurethane.

15. The method of claim 13 or 14, wherein the reacting the bifunctional poly( arylene ether) with the organic diisocyanate is by reactive extrusion.

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